0000000000240515
AUTHOR
Matthias H. Reihmann
Enzymatically catalyzed synthesis of photocrosslinkable oligophenols
The HRP-catalyzed oligomerization of cinnamoyl-hydroquinone-ester and cinnamoyl-4-hydroxyanilide led to the formation of soluble polyphenols. The oligomers were synthexized in water/1,4-dioxane and in water/acetone mixtures and characterized by NMR, FTIR and SEC. Upon UV treatment of the homogenoes films the polyphenols were crosslinked due to [2+2]-cycloadditions of the cinnamoyl functions.
Oxidative oligomerization of cyclodextrin-complexed bifunctional phenols catalyzed by horseradish peroxidase in water
The HRP-catalyzed oligomerization of hydrophobic bifunctional phenols in water was realized by the use of 2,6-di-O-methylated β-cyclodextrin. The molecular weights of the resulting oligomers were in the same region as they were reached by conventional HRP-catalyzed oligomerizations in water/dioxane-mixtures. The polymerizable moieties, maleimide and methacrylamide, were not affected during the oligomerization process, as proofed by NMR, MALDI-TOF and FT-IR measurements. It was therefore possible to get soluble functionalized oligomers, which were crosslinked via radical copolymerization with suitable components (styrene, MMA) or heating.
Oxidative Copolymerisation ofpara-Functionalized Phenols Catalyzed by Horseradish peroxidase and Thermocrosslinking via Diels-Alder and (1+3) Cycloaddition
The horseradish peroxidase- (HRP-) catalyzed polyrecombination of N-(4-hydroxyphenyl)-2-furamide (2) and 4-hydroxyphenylmaleimide (1) is described. The resulting copolymer was used to build crosslinked materials via Diels-Alder and cycloaddition reactions. We followed the enzymatic copolymerization process of an equimolar mixture of 1 and 2 using high pressure liquid chromatography (HPLC), size-exclusion chromatography (SEC) and by matrix assisted laser desorption/ionization-time of flight mass spectroscopy (MALDI-TOF MS) analysis and found that the polymerization of 2, which has a significant higher highest occupied molecular orbital (HOMO) energy, proceeds much faster. The HOMO energies o…